Metallurgical process



July 13, 1937. R. F. MEYER 2,086,570

METALLURGICAL PROCESS Filed June 29, 1955 ORE z (1) (2) 1 ADD soua ALKALI ADD SOLUTION or ALKAL/ (Na, 0H 0:? Na; 5) (Na. OHOR Na; 5)

GRIND QUASl-WET are: comm/mus ALKALI HEATTO so ro moc AGE Y mum/v or No LEACH our Mo igg ggflj V, Fe, .Si, ezc. ass/nus CONTAINING ALL THE V, Alva BASE METALS w v I I (4 I ADD soup ALKALI PART/AL RIEDUCTION (00L mow SINTERING GRIND TEHPERA TUIRE: or v, 0 uAsl-wsr M! T REM/9'25 Q x (NOTf' X) HEAT To 50' m loo'c REMOVE FHA/v0 OTHER .WlUT/O/V or v BASE MET1L,e. g.,Cu)

SUBSTANTIALLY vs etc. (Mar a x) EJIDUE con/MINING R BASE MET-4L5 RENDER QUASI- WET wm/ sowr/o/v or Aumu 0 0 (HEAT ro so ro .90 c) f Jolt/TIM or SUBSTANTIA lfi/BTB- V *rnss man He,

REOXIDATION MAY as nous A7 amvau: mm .Pb.. EIZ'HER or rm: rwo Pawns NOTED. a P e 151 5 81:25 (1H2) AND(3)-(4)AR ALTERNATIVE R E mocsounss. Y v v I mv T OR.

5663 WITNESSES BY 02 6224 {if ATTORNEYS atented July 13, l937 'UNITED, STATES PATENT OFFICE I METALLURGICAL PROCESS .Ralph F. Meyer, Freeport, Pa., assignor to Meyer Mineral Separation Company, Pittsburgh, Pa., 'a corporation of Delaware Application June 29, 1935, Serial Fla 29,113

15 Claims.

able for treatment by metallurgical methods.

For brevity of reference all such materials are contemplated by the term fore materials as used herein.

It is a major object of this invention to provide a method of treating ores and ore materials to recover ferro-alloy metals contained in them, which provides for recovery of the ferro-alloy metal in pure form substantially uncontaminated by base metal, is simple, easily performed, highly efficient, economical, affords excellent separation of ferroalloy metal from other metals contained in the ore material, such as base and precious metals, and is efiicient and more economical than the procedures heretofore applied commercially to these ends. I

A special object of the invention is to provide a simple, highly efficient and relatively inexpensive method of separating molybdenum in a state of high purity from ore materials containing it, and particularly to recover molybdenum and vanadium separately and in a state of purity such as to avoid disadvantages heretofore encountered in the art. Other objects of the invention will appear to those' skilled in the art, from the following description.

The recovery of the ferro-alloy metals from their ore materials has been attended heretofore by various disadvantageous features. A particular difliculty'that has been encountered is that the processes of recovering these metals, such as molybdenum and vanadium, for example, have been relatively expensive owing to the cost of large amounts of reagents, power and other attendant costs, and the difficult separations which previously have' not been economically avoidable. For example, those procedures have been disadvantageous because of complications involved in separating and recovering in commercially pure forms" the individual ferro-alloy metals, which have been removed concurrently from the ore. Commonly also the leach solutions are contaminated by base metals, wherefore such im-' pure solutions have necessarily had to be purified before separating and extracting the ferroalloy metals in pure forms, which has increased the difficulties and operating costs.

In a copending application, Serial No. 737,239, filed July. 2'7, 1934, I have disclosed and claimed an improved procedure of recovering ferro-alloy metals from ore materials. According to that process the material is subjected to a partial reduction treatment, cooled in an inert atmosphere to a temperature below the sintering point of the normal oxides of the ferro-alloy metals which are present, and then treated to recover metal values.

Preferably, base metals, especially lead, are separated first, after which the ferro-alloy metals are recovered, as by chloridizing, or, most suitably, the residue is reoxidized and the ferro-alloy metals recovered by alkali or acid reagents, or by flotation.

That procedure constitutes a major advance in the art because it results in substantial economies as compared with prior practice. Where a single ferro-alloy metal is present no diflicuties are encountered in its recovery, but commonly some of these ores contain morethan one ferroalloy metal. For instance, many molybdenum ores found in this country contain vanadium. The procedure disclosed in my aforesaid application may render the ferro-alloy metals concurrently soluble in the same reagents, so that although it is a distinct advance in the art, separation of the ferro-alloy metals-may still be nec e'ssary.

The present invention, on the other hand, pro-- vides, by a simple modification of the process of my aforesaid copending application, a clean and( efficient separation of, for example, molybdenum 35 and vanadium, so that the difliculty just mentioned is wholly avoided while retaining the benefits flowing from that process.

The present invention is predicated in part upon my discovery that molybdenum may be recovered directly (i. e., without preliminary treatment, such as partial reduction) and separately from other metals contained in molybdenumbearing ore materials by treating the ore material with an alkali, such as sodium hydroxide, in the presence of definitely restricted amounts of water, and subsequently leaching the ore material to extract the molybdenum therefrom; In, other words, I have found that by the combined use of (1) an alkali and (2) moisture in an amount not 5 exceeding that which renders the material quasiwet, the molybdenum can be preferentially solubilized so that the preponderant amount of it can be recovered in a quite pure form.

The term quasi-wet" as used herein applies 55 to a special condition of moistness of an ore material, in which state the material contains liquid,

such as water, in an amount sufiicient to moisten the individual ore particles adequately for the ing efiect of both gaseous and liquid reagents is Furthermore a concentrated reagent produced. solution may be used with greater benefit. These same factors render the ore in excellent condition for leaching. As further characteristics of the quasi-wet condition, such ore is not appreciably moist to sight or touch, it requires considerable hand pressure to compact it, but the compacted lump crumbles easily again. And the quasi-wet condition avoids interfering or troublesome reactions which may occur if liquid is present in excess of the quasi-wet state, i. e. if the ore is in the form of a pulp or a slime.

The amount of liquid required to produce thequasi-wet condition varies with diiierent ore materials and with their degree of sub-division but it is readily ascertainable by observation in any particular instance owing to the fact that the ore volume increases over that of the ore prior to addition of liquid, and the volume of quasiwet ore exceeds that of the ore when excess of liquid (free or movable liquid) is present, and further by the fact that free liquid between the interstices is not present. The term as applied herein contemplates the use of very small amounts, especially in a particular embodiment presently to be described, but here, too, the quasiwet characteristics described are present and recognizable.

The present invention is predicated, therefore, upon the cooperative action of alkali and the quasi-wet state in solubilizing molybdenum while keeping base metals insoluble, so that it is recovered free from base metals, and, if desired, and as is now preferred, free, or substantially free, also from vanadium. Hence it may be said that the molybdenum is preferentially solubilized in the practice of this invention.

The attainment of the quasi-wet state may be accomplished in various ways as, for example, by mixing with the ore a suflicient amount of a solution of sodium hydroxide of appropriate NaOH concentrat iog to provide enough alkali to solubilize the molybdenum and to bring the ore to the quasi-wet state. Preferably, relatively concentrated solutions of alkali are used because in general the use of concentrated soluobtained with the alkali metal hydroxides.

amount of water thus absorbed is not great but it suffices to produce a quasi-wet condition adequate for the purposes of this invention.

Various alkalies may be used in the practice of the invention, advantageously those of the alkali metals, and most suitably the alkali hydroxides and sulfides which for ease of reference are referred to in the claims as suitable alkali compounds, but the most efficient results are That is, larger amounts of sulfide are needed than where hydroxide is used and so it is usually more economical to use the hydroxide. For many purposes solutions of sodium hydroxide are preferred because of their cheapness and because of their ehiciency in action. The solution is, of course, used in an amount adapted to produce the quasiwet state and at thesame time to provide sufiicient alkali to solubilize the molybdenum. A reasonable excess of NaOH does no'harm provided the quasi-wet state is maintained. Where solid alkali is used it may be added in any conto adding the solution, 'but where solid alkali is added to dryore it is desirable to' add it to coarse ore and grind the two in a mill to convert the ore to the desired finely ground condition and intimately mix the ore and alkali. Such use of dry, or solid, alkali with grinding is very desirable in many instances for reasons more fully developed hereinafter.

An application of heat, suitably by heating the quasi-wet ore, or the ore and solid; alkali during grinding, to to 100 C. or hi her, preferably from about to 90 C., is of considerable benefit in effecting the desired result.

Advantageously also the quasi-wet mixture of ore material and alkali is aged for a period of time, prior to leaching, to complete, if need be,

the reactions involved in solubilizing the molybdenum, but more, particularly to eiTect desolubilizing of the base metals. While not absolutely necessary it is of particular benefit to conduct such a heating and aging step in the presence of an oxidizing atmosphere, such as air, either by contacting the material with air, by passing air through it, or by agitating it in air. This causes desolubilizing of the base metals to be accelerated.

This aging is particularly important where it is wished to recover the molybdenum separately from the vanadium. After heating the quasi-wet ore substantially all of the molybdenum is soluble, and part of the vanadium is also soluble.

While the two can be recovered simultaneously in a leach solution virtually free from base metals and impurities, it is desirable for most purposes that they be recovered separately. The aging step completely desolubilizes the vanadium without afiecting the molybdenum solubility, affording complete separation of the two. The vanadium may be recovered in pure forms by procedures presently to be described.

Where quasi-wetness is reached by an alkali solution the maintenance of the quasi-wet condition and the heating of the ore may be combined by treating the ore with steam, which supplies the heat desired together with sufiicient moisture to'efiiciently maintain the quasi-wet state. Air

may be added simultaneously. Such a step may be combined with agitation, ii. desired. In the practice of the invention as thus described it is possible to solubilize substantially all of the molybdenum and to separate it from any vanadium and'other metals contained in the ore; Upon leaching the treated ore there is obtained a practically pure solution of molybdenum, apparently. as sodium molybdate, containing, at most, traces of iron, zinc, arsenic, silica, lead, phosphorus and other impurities which "commonly attend these ore's.

Example 1.-As an example of the practice of the invention, and of the benefits which attend it, reference may be made to the treatment of a concentrate containing about 6.66 per cent of molybdenum oxide, MoOa, 6.72 per cent "of vanadium oxide, V205, 16 per cent of zinc, about 28 per cent of lead, 0.64 per cent of copper, 0.6 per cent of aluminum calculated as A1203, 23.55 per cent of iron calculated as FezOa, 16.5 per cent of silica,

and 1.76 Der cent of calcium calculated as Cat). The concentrate was ground to about IOO-mesh, and'the ground material was treated with a 40 per cent water solution of sodium hydroxide, suflicient solution being used 'to provide the ore with about 6 per cent of sodium hydroxide. This amount of solution rendered the ore quasi-wet, and provided suflicient alkali for the purposes of the invention. The alkali solution was added gradually to the ore while agitating and heating it. The mixture was heated 30 minutes at about 90 C., and this caused both the molybdenum and a part of the vanadium to be solubilized. The vanadium was desolubilized by then aging for 24 hours'at room temperature and in contact with .ing wetting to that suflicient to produce the quasiwet state is an important factor in the invention, reference may be made likewise to other tests in which excess of liquid was used in treating other portions of the ore just referred to. Y

Example 2.--In one such test the ore was digested 1 hour at90 C. in a 20 per cent solution of sodium hydroxide, there being used one part of ore to one part of solution. The molybdenum recovery was substantially that eifected in Example 1, but the leach solution contained 7.52 per cent of lead, a large amount of zinc, and some silica. Such amounts of lead, silica and zinc renderthe solution quite foul, and obviously they render the recovery of the molybdenum more-difficult and expensive, and may make it difllcult economically to obtain the molybdenum satisfactorily in pure form, I

Similar results were obtained using more dilute solutions of sodium hydroxide, and also using smaller amounts of. solution, although still in an amount suflicient to provide excess of liquid.

duce the quasi-wet state. 1 The material was di-' The leach solution con-,

Example 3.In another test a further amount gested. 1 hour at C. The slurry was then dried to a quasi-wet state, following which it was heated and agitated for 30 minutes while maintaining it quasi-wet, and then it was aged 24 hours, just as described in connection with Example 1. When the material was leached the results were practically the same as obtained in connection with Example 1, from which it appears that the use of the quasi-wet state in accordance with this invention provides its beneficial results even though there may initially have been present an excess of solution.

Example 4.- In still another test a further portion of the ore was digested 1 hour with a 10 per cent water solution of sodium hydroxide, using one part of ore to 0.6 part of caustic soda solution, as in Example 3. This treatment solubilized only about 60' per cent of the molybdenum, and the solution; contained also 1.7 per cent of soluble lead, together with some zinc and silica.

A comparison of Examples 3 and 4 is illustrative of the benefits of this invention. Example 4 represents the prior art methods of using excess of liquid. It resulted in incomplete extraction of the molybdenum and in the production of an impure solution. Example 3, in which the same amounts of the same materials were used as in Example 4, but in which the quasi-wet state was produced, afforded substantially complete extraction of the molybdenum in the form of a very pure solution. Thus the benefit of the'quasi-wet method which characterizes this invention will be clear from the increased extraction in purer solution and with the use of decreased amounts of reagent.

If preferred, the vanadium may be removed in good yield and in pure form by applying the process of the invention to the molybdenum-free residue obtained as described hereinabove. That is, after the molybdenum has been removed, the residue is treated with alkali in the quasi-wet state, applying heat, as described, followed by leaching. It is particularly. advantageous to make use of the embodiment in which solid alkali is ground with the dry ore, especially because the vanadium can be removed thus without preliminary removal of the base metals which, just as in removal of the molybdenum, remain insoluble. In general a rather large excess of alkali, about 200 to 400 per cent of that theoretically needed to combine with the vanadium, is needed where caustic soda is used. 1 The ore is dried after leaching the molybdenum, .the solid alkali, sodium hydroxide, preferably is added and the two are ground. The ground material is made quasi-wet, as by exposing it to moist air or steam, and the quasi-wet ore is then heated for a period, for example as in Example 6, cooled and either leached immediately, or aged to desolubilize impurities. The ore described in Example 1 was treated in this manner with recovery of 94 per cent of its vanadium content in pure solution. I

With a rather large excess of alkali present in the quasi-wet state'the vanadium remains soluble upon aging and the impurities are more completely desoiubilized.

J The addition of solid alkali to the ore, with subsequent grinding, is a desirable procedure, and it is of importance particularly where excess oi alkali is used, as in removing vanadium. F'orv instance, if a particular ore requires 30 per cent of sodium, hydroxide for extraction of its, vanadium content, a sticky and diflicultly -'workable mass would result if the alkali were added in the form of a solution. But by adding solid alkali to the ore (and drying, if necessary) and grinding the mixture excellent results are had, all such difficulties as that mentioned being removed; thereafter the necessary moistening takes place automatically by merely exposing the ground of alkali and the quasi-wet state the vanadium can" be solubilized. The large excess of alkali may be added as a solution and good results obtained but many mechanical difficulties are encountered.

Although the invention has been described thus far with reference to treatment of ores containing molybdenum, or molybdenum and vanadium, it will be understood from the foregoing description that the process provided by the invention is applicable equally to ores containing vanadium but no molybdenum.

Example 5.-A portion of the same ore, about 40 to (SO-mesh grain size, was heated to C. and to it there was added 27 per cent of solid caustic soda in stick form. The mixture was ground during" 20 minutes to about lBO-mesh, the mill being kept at a temperature of about 120 C. After cooling it was leached with water thus extracting '75 per cent of the molybdenum and 50 per cent of the vanadium in a solution substantially free from silica, lead and iron, and containing but 0.25 per cent of l ad, and 0.3 per cent of zinc. l a

As noted hereinabove, a considerable excess of sodium hydroxide should ordinarily be used to solubilize the vanadium, as much as 200 to 400 per cent excess NaOH being desirable. When such excess sodium hydroxide is present, the dry ground and heated material will have about {75 per cent of its molybdenum content and 50 per cent of its vanadium content solubilized, as indicated by Example 5. Aging of the ore under such condition of excess alkali causes no material change in M0 and V solubility but it does assist in rendering base metals and impurities insoluble, more particularly when the material is quasi-wet.

Example li -Ground material the same as described in Example 5 was exposed to air until it had absorbed 5 per cent of moisture, and it was then heated 1 hour at to C., and a sample was leached immediately, which gave a solution containing 99 per cent of the molybdenum, 94 per cent of the vanadium, 0.09 per cent of silica, 0.11 per cent of lead, and 0.17 per cent of zinc. The remainder of the material was then aged 12 hours, after when the Mo and V solubilities were approximately the same as before aging, while mere traces of lead and silica were soluble, and but'0.11 per cent'of zinc.

Erample 7.-The same ore was treated to remove the molybdenum by mixing the coarse dry material with 6 percent of flake NaOH, grinding to about 100-mesh, then moistening with 15 per cent of Water, and heating 1 hour at 90 to 100 C., followed by aging 24 hours. Upon leaching substantially all of the molybdenum was extracted in a clean solution. The residue was dried and 30 per cent of granular NaOH was added to it. .The mixture was ground to form an intimate mixture while heating the material to to C. About 50 per cent of the vanadium was then soluble together with very small amounts of Pb, Zn and SiOz. The ground material was made quasi-wet with about 6 per cent of moisture and heatedl hour at 90 to 100 C. and aged, with practically the same results as in Example 5. The dry ore can be ground cold, thenmade quasi- .wet and heated with substantially the same result.

Emample 7a.A part of the dry ground (after removal of Mo) orecontaining Na0I-I described in Example 7 was mixed with 100 per cent by weight of water (A), and another part with 50 per cent by weight of water (B). Both portions were digested 1 hour at 85 to 90 C., the volume of the slurry being kept constant by additions of water. Both portions were filtered and the solubilities determined: Portion A (100% H20): 65 percent of the vanadium was soluble together with 3 per cent of Zinc, 15 per cent of lead, and 0.9 per cent of silica. Portion B: 65 to 70 per cent of the vanadium was soluble together with much more Pb, Zn and SiOz, than in Portion A.

Example 7-b.,-Two tests were made like Portions A and B of Example 7-a, but the digested slurries were dried to quasi-wetness and heated 1 hour at 90 to 100 C., and ;then aged. The results obtained were equivalent to those obtained in Example 7.

7 It appears, therefore,.that by dry grinding the ore and NaOH together with heat, about 75 per cent of the Mo and 50 per cent of the V can be solubilized provided sufficient NaOH be present; by quasi-wetting the material substantially all the Mo and V can be solubilized. Or, by using less NaOH the Mo can be selectively solubilized, then the V can be solubilized by treating the residue with more NaOH. The excess NaOH over that needed to solubilize the V can be recovered by crystallizing out the sodium vanadate and evaporating the mother liquor to dryness andreusing the resultant NaOH.

It thus appears that the invention does not reside alone in the use of an alkali solution, but

that the quasi-wet state constitutes a critical factor which makes possible clean separation of the molybdenum and vanadium from the other metals. The exact mechanism is not fully understood, and while I do not limit myself to this explanation, it appears probable that in treating ores of the type contemplated with alkali in the recovered as desired from the leach solution, this.

being uncomplicated by" the necessity for separating it from other metals because of the purity of the solution. W

The residue remaining after molybdenum extraction may then be worked up to recover other metal values. I have found that vanadium or other ferro-alloy metals, when present, may be recovered by treating the residue 'in' accordance with the process disclosed in my copending application Serial No. 737,239, referred to hereinabove, and various details and modifications of this step will now be described. V Assuming vanadium to be present, the leached residue is subjected to a partial reduction, as by mixing it with a solid reducing agent, heating the mixture and effecting partial reduction .of ore constituents, and then cooling in a non-oxidizing, or inert, atmosphere to normal temperature, or at least to a temperature below the sinteringtemperature of the normal oxide of vanadium (V 05). In the practice of this step the ore residue (after removal of molybdenum) is intimately mixed with an appropriate amount of solid reducing agent, e. g., a carbonaceous reducing agent, advantageously coal. It is advantageous to grindthem together, for not only does this effect, the desiredintimate commingling, but also it is desirable to have :the on ground. The mixture is then heated to eifect partial reduction of ore constituents, and thereby to break up the refractory complexes. In the case of most ores reduction may be effected suitably at temperatures of about 300 C. to about 900 C. With some ores a very short heating suflices, while others may require heating for several hours, say two or three. I have found that in such instances it usually sufi'lces to bring the ore up to temperature and then give it a soaking treatment at temperature in a heat-insulated soaking chamber, or pit, for a suitable length of time, for example, one to three hours. The ore sumclently retains its temperature to eilect the desired reduction without the addition of heat during the soaking period,

If the ore becomes sintered the recovery of the metals, if not substantially precluded by the simple means characteristic of -the invention, is certainly much less efllcient. I have found also that to .avoid such sintering the ore should be intimately mixed with the reducing agent prior to elevating its temperature. .The particles of reducing agent apparently serve to hold the ore. particles apart and prevent them from sintering. Also, the more intimately the reducing agent is mixed with the ore, the better is the reduction and breaking up of the refractory complexes. The effect of these factors is especially important in. the case of ore materials high in easily fusible compounds of lead. I

After reduction the ore is carefully cooled in an inert, or non-oxidizing atmosphere, such as the reducing atmosphere of the reduction step, toroom temperature, or -a temperature below the sintering temperature of the normal oxide of the ferro-alloy metal, or metals, concerned, for ex- 1 ample, in the case of vanadium below about 658 C., the sintering temperature oi its pentoxide. The sintering point is apparently much lower in'the case of the normal oxides, so that the reduced ore should be carefully cooled in a non-oxidizing atmosphere to a lower temperature. The cooling should be continued to room temperature in contact with the inert atmosphere where the metal values are to be recov-, ered by leaching or the like methods, but where the ore is to be reoxidized, as referred to hereinafter, before the'base metals-are removed it need be cooled only to a temperature suitable therefor with avoidance of sintering. For reoxidation most of the heat necessary may be supplied by the carbon left in the material after they partial reduction. Y

- This partial reduction breaks down the min eral complexes and puts the metal valuesin a condition .for easy recovery of them. Thus, as

' described in my copending application, the vanadium may be recovered by chlorldizing, or it may be reoxidized to produce the normal oxide of vanadium, which may be leached with alkali or acid solutions, which affords a good recovery of the vanadium. Or, the quasi-wet alkali method. may best be used to recover the vanadium. However, if base metals, especially lead, are present they should be removed before leaching with NaOH solution if clean vanadium solu- Y tions are desired. If they are notpreliminarily removed the vanadium solutions will contain appreciable amounts of lead, zinc, silica, iron, copper, etc., depending on the reagent and conditions, which is undesirable.

The base metals, such as copper and lead, and

, other base metals when present, may be removed first, and this may be done'by known methods.

Advantageously it is accomplished by application of the quasi-wet principle disclosed in my earlier patents, among which are No. 1,833,682, No. 1,898,018, and others.

With ores containing lead it is desirable to remove it by a novel procedure which I have dis-' closed and claimed'in my aforesaid copending application. According to that method the ore residue after reduction and cooling is rendered quasi-wet with a solution or vapor of acetic acid at a suitable temperature, and through such use of this reagent there is rapid conversion of the lead to acetate, which is easily soluble in water.

This reagent renders the copper soluble also, but if the quasi-wet material be treated with'only enough acetic acid to combine with the lead it is possible to leach the preponderance of the lead in substantially pure solution, and particularly to effect a relatively clean separation of the lead and copper.

The acetic acid may be regenerated and the lead recovered by gassing the strong lead acetate solution with sulfur dioxide, which causes the lead to be precipitated as lead sulflte, regenerating the acetic acid for further leaching. The lead sulflte may be worked up in various ways to convert it to other lead compounda'or it may be smelted to convert it to metallic lead, thus regenerating the sulfur dioxide for use in treating become sticky, and the base metals can becompletely solubilized in one operation if desired. Also, very dilute acetic acid may be thus utilized and the reduced material then acts as a scrubbing agent whereby the acetic acid combines with the metals and the excess of water vapor over that necessary to maintain the quasi-wet condition passes out of ,the reaction chamber. Due to the temperature of 80 to 95 C.' the excess water is not permitted to condenseinto the ore and is therefore carried off completely separated from the acid. or course, some amount of water will condense into the ore to quasi-wet it, this condition being controlled by the temperature.

The ore residue remaining after such lead separation is washed, dried and again rendered quasi-wet with acetic acid, following which it is cedure, and its rapidity are especially desirable, as is also the fact that by due precaution as to the amount of aceticacid used, a substantially pure solution .of lead is obtained. Of course, if copper and the like are absent, the amount of acid used is less important. Low iron solubility results from restriction of the amount of acetic acid and from elevated temperature (80 to 95 0.), and this follows largely from quasi-wetting, which permits only restricted amounts of liquid. At a temperature of -95 C. practically no iron is solubilized. Any iron s'olubilized and in the ferric condition may be removed completely from lead acetate solution by merely boiling it.

Returning now to the recovery of vanadium, the reduced material, after removal of the lead and copper, is reoxidized at a temperature below the sintering or melting point of the normal oxide of vanadium.

Such a reoxidizing treatment may be effected by heating the reduced material in air to a temperature of about 400 or 500 'C. If preferred for any reason this reoxidation may be performed before removal of base metals, instead of after their removal as described in the foregoing illustrative embodiment.

After reoxidation the ore is rendered quasi-wet with a solution of analkali and treated as described hereinabove for the extraction of molybdenum. Here again the invention is characterized by production of clean vanadium solutions, with attendant benefits, and with recovery of the preponderant part'of the vanadium present. Removal of lead is important to this end because otherwise the recovery is less emcient. The final residue is then treated in any desired manner for recovery of any further amounts of base and precious metals which may be present,

This application is a continuation in part of my copending applicationSerial No. 746,400, filed October 1, 1934.

According to the provisions of the patent statutes, I have explained the principle of my invention and described what I now consider to represent its best embodiment. However, I desire to have it understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

I claim: a

1. That method of treating, ore material containing a metal of the group molybdenum and vanadium, comprising the steps of introducing into the ore a suitable alkali in an amount suflicient to solubilize said metal and water in an terstices between the particles, the thus moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable hand pressure to compact it, and the compacted lump crumbling easily, thereby converting said metal to soluble form, and leaching the thereby solubilized metal fromthehtreated ore. a

2. That method of treating ore material containing metal of the group molybdenum and vanadium, comprising the steps of introducing into the ore a suitable alkali in an amount sufwicient to solubilize said metal and water in an amount sufiicient to moisten the individual particles of the ore andv produce an increase in ore volume as compared with dry ore, but such that free movable liquid is absent from the interstices between the particles, the thus-moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable hand pressure to compact it, andgthe compacted lump crumbling easily, heating the'thus-moistened material and agitating it in contact with air, thereby converting the molybdenum to soluble form, cooling to normal temperature and allowing the material to stand for a period of time 'sufiicient to desolubilize water-soluble vanadium, and leaching the solubilized molybdenum from the treated ore.

3. That method of treating ore materials containing molybdenum, comprising the steps of mixing with the material a solution of alkali metal compound in an amount to provide sufiicient alkali to solubilize the molybdenum and. water in an amount suificient to moisten the individual particles of the ore and produce an increase'in ore volume as compared with dry ore, but such that free movable liquid is absent from the interstices, the thus-moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable hand pres sure to compact it, and the compacted lump crumbling easily; treating the thus-moistened material with steam, and thereby converting the molybdenum to soluble form, and leaching the solubilized molybdenum from the treated ore.

4. In a process of treating ore materials to ,to compact it, and the compacted lump crumbling easily, heating the mixture to solubilize said metal and leaching the ore to recover said metal therefrom.

5. In a process of treating ore materials to recover metal values, that combination of steps comprising grinding the dry ore material with a solid alkali in an amount suiiicient to solubilize the molybdenum contained in the ore and introducing" into the mixture water in an amount suflicient to moisten the individual particles of the ore and produce an increase in ore volume as compared with dry ore, but such that free movable liquid is absent from the interstices, the

thus-moistened ore being of loose, open structure,

not appreciably wet to sight or touch, requiring considerable hand pressure to compact it, and the compacted lump crumbling easily, heating the mixture to solubilizemolybdenum contained I comprising'mixing the ore material with a solution of a suitable alkali in an amount such as to v provide suflicient alkali to solubilize molybdenum contained in the ore and to provide water in an amount sufficient to produce a condition in which the individual particles ofthe' are are moistened rial being heated to about 60 to 90 C. in the dry ore, but free movableliquid is, absent from the interstices, and the ore is of loose, open structure, not appreciably wet to sight. or touo requires considerable hand pressure to comp ct it, and the compacted lump crumbles easily, .he ting the'mixture to solubilize molybdenum, cooling to normal temperature, holding the ore for a period of time sufficient to desolubilize water-soluble vanadium, leaching the ore to extract molybdenum, drying the leached ore and grinding it with an excess of a solid alkali, introducing into the dry and ground ore water in an amount suificient 1 to reproduce said condition, heating the mixture to solubilize vanadium, and dium from the ore.

7. That method of separately recovering molybdenum and vanadium from ore materials containing them, comprising mixing the finely divided orewith a solution of a suitable alkali in an amount such as to provide alkali sufilcient to solubilize molybdenum and to provide water in an amount suflicient to produce a condition in which the individual particles of the ore are moistened and an increase in ore volume is produced as compared with dry ore, but free movable liquid is absent from the interstices, and the ore leaching the vana- I is of loose, open structure, not appreciably wet to sight or touch, requires considerable hand pressure to compact it, and the compacted lump crumbles easily, allowing the moistened ore to .stand for a period of time suificient to render insoluble ore constituents other -than molybdenum, leaching the molybdenum from the ore, effecting partial reduction of ore constitutents in the leached residue, cooling under non-oxidizing temperature oi the normal oxide of vanadium, removing lead from the material, reoxidizing the vanadium, adding a solution of alkali metal compound to reproduce said condition, and leaching to recover said vanadium;

8. That method of separately recovering molybdenum and vanadium from ore materials containing them, comprising (1) introducing intothe finely divided ore material a suitable alkali in an amount suflicient to solubilize molybdenum and liquid in an amount sumcient to produce a condition in which the individual particles of the ore are moistened and an increase in ore volume is produced as compared with dry ore, but free movable liquid is absent from the interstices, and the ore is of loose, ope'n structure, not appreciably wet to sight or touch, requires considerable hand pressure to compact it, and the compacted lump crumbles easily, agitating the thus-moistened mixture in contact with air, and then leaching out the molybdenum; and (2) providing an intimate mixture of the leached residue with solid reducing agent, heating themixture and effecting partial reduction'of' ore constituents, cooling under non-oxodizing conditions to a temperature below the sintering temperature of the normal oxide of vanadium, removing lead irom the thus-treated ore, heating to reoxodizevanadium oxide, mixing with a solution of alkali metal compound in'an amount to reproduce said condition, agitating the thusmoistened material in contact with air, and,

leaching the vanadium, the leach solutions being substantially free'from base metals. v

molybdenum recovery step. 11. A process according to claim 8, the material being heated to about 60 to 90 C. in the molybdenum recovery step.

' 12. That method of treating ore material containing metal of the group molybdenum and vanadium, comprising the steps of introducing into the ore an alkali hydroxide in an amount sufiicient to solubilize said metal and water in an amount suiiicient to moisten the individual particles of the ore and produce an increase in ore volume as compared with dry ore, but such that free movable liquid is absent from the interstices between the particles, the thus-moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable hand pressure to compact it, and the compacted lump crumbling easily, heating the thus-moistened material to a temperaturesuflicient to solubilize said metal while not solubilizing substantial amounts of other metals, and leaching the treated ore and thereby recovering said metal in solution substantially free from base metal.

13. That method of treating ore material containing metal of the group molybdenum and vanadium, comprising the steps of introducing into the ore an alkali hydroxide in an amount sufiicient to solubilize said metal and water in particles of the ore and produce an increase in ore volume as compared with dry are, but such that free movable liquid is absent from the interstices between the particles, the thus-moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable hand pressure to compact it, and the compacted lump crumbling easily, heating the thus-moistened material and agitating it in contact with air for a' period of time suflicient to convert said metal to soluble form and desolubilize-other metals, and leaching the treated ore and thereby re- ,eovering said metal in substantially pure soluion.

14. That method of treating ore material containing molybdenum and vanadium, comprising the steps of introducing into the ore an alkali hydroxide in an amount suflicient to solubilize the molybdenum and water in an amount suflicient to moisten the individual particles of the ore and produce an increase in ore volume as compared with dry ore, butsuch that free movable liquid is absent from the interstices between the particles, the thus-moistened ore being of loose, open structure, not appreciably wet to sight or touch, requiring considerable. hand pressure to compact it, and the compacted lump crumbling easily, heating the moistened material to a temperature suflicient to convert the molybdenum to soluble form while not solubilizing substantial amounts. of other metals, leaching the treated ore and recovering molybdenum in solution substantially free from vanadium and base metal, bringing the residue to the aforesaid moistened condition and adding alkali hydroxide in an amount in excess of that theoretically equivalent to the vanadium, heating the moistened ore, then leaching and recovering vanadium in solution substantially free from base metal.

15. That method of treating ore material containing metal of the group molybdenum and vanadium, comprising the steps of introducing into the ore and alkali hydroxide in a: amount suflicient to solubilize said metal and water in particles oi the ore and produce an increase in ore volume as compared with dry ore, but such that free movable liquid is absent from the interstices between the particles, the thus-moistened. ore being of loose,' open structure, not appreciably wet to sight or touch, requiring considerable hand I N 083,570 an amount sumcient to moisten the individual 

